TW201119738A - Method for manufacturing large-diameter titanium-silicon molecular sieve and method for manufacturing cyclohexanone oxime using such a molecular sieve - Google Patents

Abstract

A method for manufacturing large-diameter titanium-silicon molecular sieve comprises preparing first grade crystalline particle molecular sieve dispersion liquid; adding flocculant and coagulant aid to the dispersion liquid to flocculate the particles and form a particle-flocculated solution; mixing the particle-flocculated solution with synthetic rubber of titanium-silicon template; and performing a hydrothermal step. The titanium-silicon molecular sieve manufactured with this method has an average particle diameter greater than 5 micrometer and can be used as a catalyst, whereby when used in manufacturing cyclohexanone oxime, it provides high conversion rate and selection rate and also features the advantage of easy filtration for recycling.

Description

201119738, VI, invention description:

TECHNICAL FIELD OF THE INVENTION The present invention relates to a process for producing a titanium-bismuth molecular sieve, and more particularly to a process for producing a large-diameter titanium-ruthenium molecular sieve. [Prior Art] The crystalline titanium-germanium molecular sieve system introduces titanium atoms into the network structure of cerium oxide, and has a crystal form of an MFI structure, also known as a TS-1 molecular sieve. However, this molecular sieve has been widely used as a ruthenium in an oxidation reaction using hydrogen peroxide as an oxidizing agent, and its preparation method has been disclosed in U.S. Patent No. 4,410,501. However, the molecular sieve particles produced by this method are approximately 0.2 microns. However, 0.2 micron catalysts are extremely challenging in chemical process applications such as the use of cyclohexanone, ammonia, and hydrogen peroxide to produce cyclohexanone oxime using a titanium ruthenium molecular sieve as a catalyst. Therefore, the inventors of the following are all committed to the development of techniques for increasing the size of molecular sieves. U.S. Patent Nos. 5,500,199, 6,106,803 and 6,524,984 teach the polymerization of small particle catalysts by inorganic binders and spray-drying granulation. This method can increase the catalyst particles but has catalytic activity. The base is covered by the adhesive and the reactive group is diluted to have insufficient reactivity and it is necessary to increase the amount of the catalyst to maintain the same catalytic effect. Therefore, how to overcome the above shortcomings has become an urgent issue. There is still a need in the industry for a method for preparing a titanium-germanium molecular sieve having a large particle size and high activity, which overcomes the difficulties of conventional molecular sieve recovery, enhances the efficiency of hydrogen peroxide use, and is suitable for industrial applications. SUMMARY OF THE INVENTION In view of the above-mentioned shortcomings of the prior art, the present invention provides a method for producing a large 3 11132] 201119738 (^ by Titanium-Shixi molecule), including · preparing a first-order crystalline particle molecular master white it a flocculating agent and a coagulant are added to the dispersion to form a granule solution; the aggregated granule solution is mixed with a titanium ruthenium templating agent; and a hydrothermal step is carried out. The method of the present invention is formed. The titanium-Shixi molecule has an average particle diameter of 5 micrometers or more. As a catalyst for the fat, it can not only achieve high conversion rate and selectivity, but also has the advantages of easy filtration and separation. MODES OF THE INVENTION The following is a specific example to illustrate the implementation of the author. The technical person can easily reveal the advantages and functions of the content disclosed in this specification. This creation can also be applied in other different ways. 'Immediately' can be modified and changed before the technical idea disclosed in this creation. The method of the present invention uses the hydrothermal un-molecular sieve powder (TS), SU. a combination thereof) as a molecular sieve of the first-stage crystal particles, dispersing the powder of the molecular sieve molecular sieve in water to form a dispersion, and then adding the I and the coagulant to aggregate the particles to form an aqueous solution of the aggregated particles. The aqueous solution of the aggregated particles and the titanium plate are synthesized and the mixture is sealed in a Teflon-lined stainless steel pressure-resistant tank to prepare a hydrothermal step. The molecular sieve of the H-grade crystal is difficult to synthesize with the Qin·矽杈 plate The weight ratio of the glue mixture is in the range of (7) to the general, preferably between 1:]G to 1: coffee, and more preferably between: H) to::, and more preferably between 1: 11.6 to i: 167. The flocculating agent used in the process of the present invention is a high-molecular flocculant. More specifically, 1 321 4 201119738, the flocculant of the present invention may be derived from a cationic flocculant, an anionic flocculant, an amphoteric flocculant or a combination thereof. Examples of the cationic flocculant include quaternary ammonium salt polymers such as dimethyl-diallyl ammonium chloride polymer or polymethylammonium methacrylate polymer, polyethylene or polyethylene. °, or a combination thereof; examples of anionic flocculation swords include sodium polyacrylate and propylene yttrium ammonium copolymers, sodium acrylate and propylene yttrium ammonium copolymers or combinations thereof; examples of amphoteric flocculants include quaternary acrylic acid and sodium acrylate Copolymer. In general, the two molecules of flocculant used in the process of the present invention have an average molecular weight of at least 100,000 or more, preferably 100,000 to 2 Å, face, 〇〇〇. The flocculant can be added as an aqueous solution. Usually, the concentration (% by weight) of the aqueous flocculant solution is in the range of 0,1炱1% by weight, preferably 0.2 to 0.8% by weight, and more preferably in the range of 0.3 to 0.6% by weight. The flocculating agent is used in an amount of from 0.0001 to 〇.05 g, preferably from 0.0001 1 0.03 g, more preferably from 0.001 to 0.025 g, based on 100 g of the titanium-ruthenium template. The coagulant used in the present invention may be a citric acid vinegar, a polyethoxy decane or a cerium oxide colloidal solution. Examples of the phthalic acid ester include tetradecanoic acid, tetrahexyl phthalate, tetrapropyl phthalate, tetrabutyl phthalate or a combination thereof; examples of the polyethoxy decane include ES-28 (n=l to 2), ES-32 (n=3 to 4), ES-40 (n=4 to 5) or a combination thereof; and examples of the cerium oxide colloidal solution include Ludox AS available from DuPont -40, Ludox, Ludox AM-30, Ludox TM-40, Ludox TM-50, Ludox A^ [~3〇, Ludox HS-30, Ludox HS-40 or a combination thereof. In the preparation method of the present invention, the coagulant is used in an amount of 100 g of a titanium-ruthenium template to synthesize 201119738 f〇f using a coagulant of 0.1 to 6 g, preferably 0.1 to 3 g of a coagulant. . In a specific example, the titanium (4) plate synthetic gel used in the process of the present invention is prepared by the following method: First, a titanium source (for example, tetradecane f (tetra), titanium trichloride, titanium hydride) The titanium source is placed in the nitrogen-sealed single-necked bottle. The system temperature is then lowered to the well and a solvent (eg, anhydrous isopropanol or water) is placed in the above-mentioned II single-necked flask for -15 minutes. Then, using equal pressure addition, leakage: the source of lanthanum (for example, tetraalkyl phthalate, yttrium, cerium sol) is dropped into a nitrogen-sealed single-necked bottle, and the mixing is continued after the completion of the dropwise addition, for a long time! hour. After the mixture was mixed, the templating agent (for example, tetrapropylammonium hydroxide) was dropped into a nitrogen-sealed single-necked flask by a whisker addition funnel, and the hydrazine was continuously continued for 1 hour. Finally, after the temperature of the system is returned to normal temperature, the bath is removed, and a titanium-ruthenium template synthetic rubber is obtained (for example, the alcohol is removed under the condition of rib.c for 2 hours). In general, in the reaction process for producing the enamel templating agent synthetic rubber of the present invention, the molar ratio of the titanium source and the cerium source used is 0.005:1 to 0.06:1, preferably 〇〇15:j. To 〇〇 5. More preferably 0.02 : i to 0.045 : !. The molar ratio of the templating agent used and the shixi source is 0.1: i to 〇·5: 丨, preferably 〇 15 : 1 to Μ · 卜 * more preferably 0·2: 1 m 1 . The molar ratio of anhydrous isodecyl alcohol and Shixiyuan used is from 1:1 to 4.5:1, preferably from 18:i to 3 5 . /, more preferably from 2.2:1 to 3: water used The molar ratio of the stone and the eve of the eve is 10. j to 80: 1, preferably 2 〇: 丨 to 6 〇: 丨, more preferably Deng: 1 to. 111321 6 201119738 The method of the invention, the water heat The step water is used as a medium, and an appropriate temperature is applied to generate pressure in the closed reactor to carry out the reaction. In the example of the invention, the present invention utilizes a hydrothermal method to utilize a stainless steel pressure tank of the iron gas cylinder as a reactor, and the reactor is screwed and sealed, and then placed in a heating furnace for reaction to prepare a large particle. Diameter Titanium-Stone molecular sieve In general, the temperature of the hydrothermal step carried out by the process of the present invention is between 1 Torr and 22 Torr C, preferably 15 G ° C to 18 G ° C. The hydrothermal step has a time ranging from 72 hours to 24 G hours, preferably from 12 () hours to 192 hours. This! X month clothing method can also be completed after the hydrothermal step, the solid and liquid solid parts are washed with water to neutral, and then dried and calcined to obtain; the clothes have been turned into large grains; Shi Xi molecule _ catalyst. In general, the calcination temperature is between 450 C and 650 ° C, preferably 5 () (rc to 5 thieves, the calcination time is between 6 hours and then between hours, preferably 12 hours). To % hours.

The titanium-germanium molecular sieve prepared by the method of the invention may have an average particle diameter of more than micrometers. 'It is suitable for use in the process for preparing cyclohexanone bricks as an angle! The invention also provides a method for preparing a ring gambling method. The large-sized 彳H7 molecular sieve obtained by the method of the t-month is used as a catalyst, and reacted with cyclohexanone, ammonia, and hydrogen peroxide under dissolved conditions to produce a 3 clear product. Usually, the reaction is carried out in a dust of 1 atmosphere > 1 or higher. Lower, in the temperature range of 40 C to 110 C, preferably 5 〇. 〇 〇 to 9 〇 dry circumference to carry out the reaction. In the reaction, the large particles used by the molecular sieves account for (.! to (1) to 5% by weight of the total amount of the reactants. The molar ratio of ammonia to ring (10) is 2:1 to Π1321 7 201119738 . · preferably 1.4 : 1 to 1.8 : 1 ; the molar ratio of hydrogen peroxide to cyclohexanone is 0.7 : 1 to 2.0 : 1 Preferably, it is from 1.0:1 to 1.5:1. The hydrogen peroxide concentration used may be from 30% to 50%, and the hydrogen peroxide feed may be gradually added to the above reaction system as the reaction time increases. The reaction for producing cyclohexanone oxime of the present invention can be carried out in the presence of a solvent, and generally a polar solvent such as an alcohol, a ketone or water is used, and among them, an alcohol such as a butanol is preferred. The following is illustrative of various embodiments of the method of the invention and is not intended to limit the scope of the invention. Preparation Example 1 A 500 ml round bottom flask was first sealed with nitrogen in a vacuum system, and 1.98 g of tetra-n-butyl titanate was placed in a nitrogen-sealed round bottom flask, and the temperature was cooled to 5 °C. Next, 20 g of anhydrous isopropanol was poured into the above nitrogen-sealed round bottom flask in a syringe while stirring was started. After the temperature was equilibrated, 30 g of tetraethyl phthalate was taken and added dropwise to a nitrogen-sealed round bottom flask with an equal pressure feeding system, and the mixture was stirred for 1 hour after the completion of the dropwise addition. A solution of 28 g (40%) of tetra-n-propylammonium hydroxide in water was added dropwise to the nitrogen-sealed round bottom flask in an isostatically charged system, and the mixture was stirred for 1 hour after completion of the dropwise addition. After the system was warmed to room temperature, it was stirred for another hour. Finally, after removing the alcohol for 2 hours at 80 ° C, water was added to a total weight of 100 g to complete the titanium-crushing template synthetic rubber. Comparative Example 1 The titanium-ruthenium template synthetic rubber obtained in Preparation Example 1 was sealed in iron fluoride 8 111321 * 201119738 . The dragon-lined stainless steel pressure tank was heated at 170 ° C for 120 hours to separate the solid from the liquid. The solid portion was washed with pure water to neutrality. After drying at 100 ° C and calcination at 500 ° C for 24 hours, a control catalyst sample 1 (a titanium-germanium molecular sieve having an average particle diameter of 1.1 μm and a median diameter (d50) of 0.5 μM) was obtained. Example 1 0.8 g of uncalcined titanium-rhenium molecular sieve TS-1 was taken and dispersed in 40 ml of water by stirring, and 3.5 ml of 0.5% by weight of an anionic® flocculant (sodium acrylate and acrylonitrile copolymer) was added. An aqueous solution having a molecular weight of 15.000.000 to 20,000,000) was stirred for 1 hour, and then 1.5 g of tetradecyl phthalate was added thereto, followed by stirring for 1 hour to form a suspension of aggregated particles. The above aggregated particle suspension was mixed with 100 g of the titanium-ruthenium template synthetic rubber of Preparation Example 1 and stirred for 1 hour, and then the mixture was sealed in a Teflon-lined stainless steel pressure-resistant tank, and heated at 170 ° C for 120 hours. After separating the solid and the liquid, the solid portion was washed with pure water to neutrality, and dried at 100 ° C for 24 hours at 500 ° C to obtain a titanium-germanium molecular sieve sample 1. (The average particle diameter was 24.2 μm, and the median diameter (d50) was 15.3 μm.) Example 2 0.7 g of uncalcined titanium-rhenium molecular sieve TS-1 was taken and dispersed in 40 ml of water by stirring. 1.5 ml of 0.5% by weight of an anionic flocculant (sodium acrylate and propylene yttrium ammonium copolymer, average molecular weight of 15.000 to 20,000,000) aqueous solution, after stirring for 1 hour, 0.43 g of ES-40 was added, and stirring was further carried out for 1 hour to form aggregated granules. suspension. 9 111321 201119738 The above aggregated particle suspension was mixed with 100 g of the titanium-ruthenium template synthetic rubber of Preparation Example 1 and stirred for 1 hour, and then the mixture was sealed in a Teflon-lined stainless steel pressure-resistant tank at 170 ° C. After heating for 120 hours, the solid was separated from the liquid, and the solid portion was washed with pure water to neutrality, dried at 1 ° C and calcined at 500 ° C for 24 hours to obtain a titanium-ruthenium molecular sieve sample 2. (The average particle diameter was 8.9 μm, and the median diameter (d50) was 8.24 μm.) Example 3 0.7 g of uncalcined titanium-rhenium molecular sieve TS-1 was used, dispersed in 40 ml of water with stirring, and 0.2 ml was added. An aqueous solution of 0.5% by weight of an anionic flocculant (sodium acrylate and propylene yttrium ammonium copolymer having an average molecular weight of 15,000,000 to 20,000,000) was stirred for 1 hour, and then 0.43 g of ES-40 was added, and stirred for 1 hour to form an aggregated particle suspension. The above aggregated particle suspension was mixed with 100 g of the titanium-ruthenium template synthetic rubber of Preparation Example 1 and stirred for 1 hour, and then the mixture was sealed in a Teflon-lined stainless steel pressure-resistant tank at 215 ° C. After the separation of the solid and the liquid, the solid portion was washed with pure water to neutrality, dried at 10 ° C and calcined at 500 ° C for 24 hours to obtain a titanium-germanium molecular sieve sample 3. (The average particle diameter was 14.7 μm, and the median diameter (d50) was 11.9 μm.) Example 4 0.7 g of uncalcined titanium-rhenium molecular sieve TS-1 was used, dispersed in 40 ml of water with stirring, and 1.5 ml was added. 0.5% by weight of anionic flocculant (sodium acrylate and propylene copolymer, average molecular weight of 30 111321 201119738, 15.000.000 to 20,000,000) aqueous solution, added after stirring for 1 hour

I 1.008 g of ES-40 was stirred for an additional hour to form an aggregated particle suspension. The above aggregated particle suspension was mixed with 100 g of the titanium-ruthenium template synthetic rubber of Preparation Example 1 and stirred for 1 hour, and then the mixture was sealed in a Teflon-lined stainless steel pressure-resistant tank, and heated at 170 ° C for 120 hours. After separating the solid and the liquid, the solid portion was washed with pure water to neutrality, dried at 10 ° C and calcined at 500 ° C for 24 hours to obtain a titanium-germanium molecular sieve sample 4. (Average particle diameter was 8.4 μm, and the median diameter (d50) was 7.8 μm.) Example 5 8.64 g of uncalcined titanium-rhenium molecular sieve TS-1 was taken and dispersed in 40 ml of water with stirring, and 1.5 ml was added. 0.5% by weight of an anionic flocculant (copolymer of sodium acrylate and acrylonitrile, average molecular weight of 15.000.000 to 20,000,000) aqueous solution, after stirring for 1 hour, 0.43 g of ES-40 was added, and stirring was further carried out for 1 hour to form agglomerated particles. liquid. Φ The above aggregated particle suspension was mixed with 100 g of the titanium-ruthenium template synthetic rubber of Preparation Example 1 and stirred for 1 hour, and then the mixture was sealed in a Teflon-lined stainless steel pressure-resistant tank at 160 ° C. After the solid was separated from the liquid, the solid portion was washed with pure water to neutrality, dried at 100 ° C and calcined at 500 ° C for 24 hours to obtain a titanium-ruthenium molecular sieve catalyst sample 5. (The average particle diameter was 5.9 μm, and the median diameter (d50) was 5.3 μm.) Example 6 0.6 g of uncalcined titanium-rhenium molecular sieve TS-1 was taken in a stirring manner 11 111321 201119738 . In ml of water, add 0.2 ml of a 0.5% by weight aqueous solution of cationic flocculant (dimethyl-diallylammonium chloride polymer, average molecular weight of 8,000,000 to 12,000,000). After stirring for 1 hour, add 0.43 g of ES-40. The agglomerated particle suspension was formed by stirring for 1 hour. The above aggregated particle suspension was mixed with 100 g of the titanium-ruthenium template synthetic rubber of Preparation Example 1 and stirred for 1 hour, and then the mixture was sealed in a Teflon-lined stainless steel pressure-resistant tank, and heated at 170 ° C for 120 hours. After separating the solid from the liquid, the solid portion was washed with pure water to neutrality, dried at 10 ° C and calcined at 500 ° C for 24 hours to obtain a titanium-germanium molecular sieve sample 6. (The average particle diameter was 15.3 μm, and the median value of the particle diameter (d5〇) was 13.1 μm.) Example 7 0.6 g of uncalcined cerium molecular sieve S-1 was taken, and it was dispersed in 40 ml of water by stirring, and 0.2 was added. An aqueous solution of 0.5% by weight of an anionic flocculant (sodium acrylate and propylene yttrium ammonium copolymer, average molecular weight of 15,000,000 to 20,000,000) was added, and after stirring for 1 hour, 0.43 g of ES-40 was added, and stirring was further carried out for 1 hour to form an aggregated particle suspension. The above aggregated particle suspension was mixed with 100 g of the titanium-ruthenium template synthetic rubber of Preparation Example 1 and stirred for 1 hour, and then the mixture was sealed in a Teflon-lined stainless steel pressure-resistant tank, and heated at 170 ° C for 120 hours. After separating the solid and the liquid, the solid portion was washed with pure water to neutrality, dried at 100 ° C and calcined at 500 ° C for 24 hours to obtain a titanium-germanium molecular sieve sample 7. (average particle diameter was 12.6 μm, median diameter (d50) was 9.9 μm) 12 111321 201119738 , Example 8 8.64 g of uncalcined cerium molecular sieve Sl was taken, dispersed in 40 ml of water with stirring, and 1.5 ml was added. An aqueous solution of 0.5% by weight of an anionic flocculant (sodium acrylate and propylene yttrium ammonium copolymer having an average molecular weight of 15,000,000 to 20,000,000) was stirred for 1 hour, and then 0.43 g of ES-40 was added, and stirred for 1 hour to form an aggregated particle suspension. The above aggregated particle suspension was mixed with 100 g of the titanium-ruthenium template synthetic rubber of Preparation Example 1 and stirred for 1 hour, and then the mixture was sealed in a Teflon® lined stainless steel pressure tank, and heated at 170 ° C. After the solid was separated from the liquid, the solid portion was washed with pure water to neutrality, dried at 10 ° C and calcined at 500 ° C for 24 hours to obtain a titanium-germanium molecular sieve sample 8. (The average particle diameter is 10.4 μm, and the median diameter (d5〇) is 8.1 μm.) Example 9 2.16 g of uncalcined cerium molecular sieve S-1 was taken and dispersed in 40 ml of water by stirring. 1.5 ml of 0.5% by weight of an anionic flocculant (sodium acrylate and propylene yttrium ammonium copolymer, average molecular weight of 15,000,000 to 20,000,000) aqueous solution, after stirring for 1 hour, adding 1.06 g of AS-40, and stirring for 1 hour to form an aggregated particle suspension . . . The above aggregated particle suspension was mixed with 100 g of the titanium-ruthenium template synthetic rubber of Preparation Example 1 and stirred for 1 hour, and then the mixture was sealed in a Teflon-lined stainless steel pressure-resistant tank, and heated at 170 ° C for 120 hours. After separating the solid from the liquid, the solid portion was washed with pure water to neutrality, dried at 100 ° C and calcined at 500 ° C for 24 hours to obtain a titanium-germanium molecular sieve sample 9. (Average 13 111321 201119738 Particle size 9.3 microns, median particle size (d50) is 6.9 microns) Example 10 2.16 grams of uncalcined cerium molecular sieve S-1 was taken and dispersed in 40 ml of water with stirring. Add 1.5 ml of 0.5% by weight of an anionic flocculant (sodium acrylate and propylene yttrium ammonium copolymer, average molecular weight of 15.000.000 to 20,000,000) aqueous solution. After stirring for 1 hour, add 0.4244 g of tetramethyl phthalate and stir for another hour. That is, an aggregated particle suspension is formed. The above aggregated particle suspension was mixed with 100 g of the titanium-ruthenium template synthetic rubber of Preparation Example 1 and stirred for 1 hour, and then the mixture was sealed in a Teflon-lined stainless steel pressure-resistant tank, and heated at 170 ° C for 120 hours. After separating the solid and the liquid, the solid portion was washed with pure water to neutrality, dried at 1 ° C and calcined at 500 ° C for 24 hours to obtain a titanium-germanium molecular sieve sample 10. (The average particle diameter was 6.5 μm, and the median diameter (d50) was 5.7 μm.) Example 11 2.16 g of uncalcined cerium molecular sieve S-1 was taken, and it was dispersed in 40 ml of water by stirring, and 1.5 ml was added. 0.5% by weight of an anionic flocculant (sodium acrylate and propylene yttrium ammonium copolymer, average molecular weight of 15.000 to 20,000,000) aqueous solution, after stirring for 1 hour, 0.4180 g of tetraethyl phthalate was added, and stirring was further carried out for 1 hour to form agglomeration. Particle suspension. The above aggregated particle suspension was mixed with 100 g of the titanium-xyl mold 14 111321 201119738 of the preparation example 1 and the plate synthetic rubber was mixed for 1 hour, and then the mixture was sealed into the iron scorpion dragon.

I Lining stainless steel pressure tank, water heating at 170 ° C for 120 hours, separating the solid and liquid, washing the solid part with pure water to neutral, drying at l ° ° C and 500 ° C simmering 24 The titanium-germanium molecular sieve sample 11 was obtained in an hour. (The average particle diameter was 8.2 μm, and the median diameter (d50) was 6.6 μm.) Example 12 0.6 g of uncalcined cerium molecular sieve S-1 was taken and dispersed in 40 ml of water by stirring, and 0.2 was added. 0.5% by weight of a cationic flocculant (dimercapto-diallylammonium chloride polymer, 8,000,000 to 12,000,000) aqueous solution, after stirring for 1 hour, 0.43 g of ES-40 was added, and stirring was further carried out for 1 hour to form agglomerated particles. liquid. The above aggregated particle suspension was mixed with 100 g of the titanium-ruthenium template synthetic rubber of Preparation Example 1 and stirred for 1 hour, and then the mixture was sealed in a Teflon-lined stainless steel pressure-resistant tank, and heated at 170 ° C for 120 hours. After separating the solid from the liquid, the solid portion was washed with pure water to neutrality, dried at 100 ° C and calcined at 500 ° C for 24 hours to obtain a titanium-germanium molecular sieve sample 12. (Catalyst having an average particle diameter of 8.5 μm and a median diameter (d50) of 7.5 μm) Example 13 8.64 g of uncalcined cerium molecular sieve S-1 was taken and dispersed in 40 ml of water by stirring. Add 1.5 ml of a 0.5% by weight aqueous solution of cationic flocculant (dimercapto-diallylammonium chloride polymer, 8,000,000 to 12,000,000), stir for 1 hour, then add 1.061 g of AS-40, 15 111321 201119738 and stir for another hour. That is, an aggregated particle suspension is formed. The above aggregated particle suspension was mixed with 100 g of the titanium-ruthenium template synthetic rubber of Preparation Example 1 and stirred for 1 hour, and then the mixture was sealed in a Teflon-lined stainless steel pressure-resistant tank, and heated at 180 ° C for 120 hours. After separating the solid and the liquid, the solid portion was washed with pure water to neutrality, dried at 1 ° C and calcined at 500 ° C for 24 hours to obtain a titanium-germanium molecular sieve sample 13. (Average particle diameter was 9.7 μm, and the median value (d50) of the particle diameter was 7.6 μm.) Example 14 A sample of the titanium-germanium molecular sieve formed in the above Comparative Example 1 and Examples 1 to 13 was used as a catalyst to carry out cyclohexanone. Preparation of sputum to assess its activity. First, 0.55 g of the catalyst sample was placed in a three-necked flask, and 5 g of cyclohexanone and 5.43 g of 28% aqueous ammonia were added, and a condenser and a stirring system were installed. After the reaction temperature was raised to 60 ° C, 5.43 g of a 35 wt% aqueous solution of hydrogen peroxide was added stepwise to the reaction time to carry out a reaction of cyclohexanone. One hour after the completion of the hydrogen peroxide feed, each catalyst was separated from the reaction liquid, and each of the separated reaction liquids was subjected to analysis of cyclohexanone oxime. The results of the analysis are shown in Table 1: 16 111321 201119738 Table 1 *CAnoe *S〇xime/Anoe ***CH2〇2 ****S〇xiinee2〇2 Average particle size (micron) Comparative Example 1 99.75% 98.28% 99.91% 88.75% 1.1 Example 1 99.27% 99.99% 99.26% 91.40% 24.2 Example 2 99.25% 99.57% 99.53% 90.31% 8.9 Example 3 99.63% 99.25% 98.92% 90.87% 14.7 Example 4 99, 14% 99, 66% 99.99% 89.82% 8.4 Example 5 99.35% 99.52% 99.36% 90.15% 5.9 Example 6 99.67% 99.03% 98.97% 91.50% 15.3 Example 7 99.02% 99.24% 99.97% 89.39% 12.6 Example 8 99.21% 98.49% 99.21% 89.50% 10.4 Example 9 99.53% 98.92% 99.35% 90.48% 9.3 Example 10 98.65% 98.37% 98.79% 90.30% 6.5 Example 11 97.49% 98.89% 97.84% 90.41% 8.2 Example 12 99.40% 98.84% 98.89% 92.20% 8.5 Example 13 99.20% 99.21% 99.52% 89.95% 9.7 *: cAn()e=cyclohexanone conversion rate=cyclohexanone consumption mole number/cyclohexanone input mole number χίοο% : s0xime/Alloe=cyclohexene Ketone oxime selectivity = cyclohexanone oxime production mole number / cyclohexanone consumption mole number xl00% ***: cH202 = hydrogen peroxide conversion rate = hydrogen peroxide consumption mole number / double oxygen Input Moir χίοο% : S0xime/H202 = Hydrogen peroxide selectivity = cyclohexanone oxime yield Molar number / hydrogen peroxide consumption Molar number χίοο% 17 111321 201119738 t In summary, the invention has a large particle size of 4 points per The large-size granules that are beneficial to industrial applications are indeed only the knives, and the large-sized molecular sieves prepared according to the method of the present invention have a high catalytic activity, and are made up of 8 m according to the preparation method of the medium. It is produced in such a way as a catalyst, which has the advantages of clothing and clothing, the choice of the name of the Jiangnan, the more impressive and the high rate of hydrogen peroxide, and the advantages of easy recycling. The above description and examples are merely illustrative of the principles of the invention and are not intended to limit the invention. The scope of protection of the present invention should be as set forth in the scope of the patent application to be described later. Figure [Simple description of the diagram] [Explanation of main component symbols] Benefits. 111321 18

Claims (1)

201119738 VII. Patent application scope: A method for preparing a large-diameter titanium-bismuth molecular sieve, comprising: preparing a dispersion of a first-stage crystalline particle molecular sieve; adding a flocculant and a coagulant to the upper knife/night to make the particles aggregate Forming agglomerated particle solution; mixing δ the 4 wood particle solution and titanium 矽 矽 template to synthesize hydrothermal step 2. According to claim 1 of the patent item, the first stage crystal granule molecular sieve is selected from the Guns 4 are not available in titanium-germanium molecular sieve powder, cerium molecular sieve powder or a combination thereof. 3. The method according to claim 1, wherein the flocculating agent is selected from the group consisting of: a flocculant selected from the group consisting of a cationic flocculant 'anionic flocculant and an amphoteric flocculant. (The method of claim 1, wherein the flocculating agent is selected from the group consisting of: one or more selected from the group consisting of dimethyl diallyl chloride deuterated polymer, and methyl methacrylate trimethylammonium ethyl vinegar A flocculant of a copolymer of a polymer, a polyethylammonium, a polyethylene, a bite, a copolymer of polypropylene and propylene, a copolymer of acrylic steel and propylene, and a copolymer of quaternary ammonium acrylate and sodium acrylate. 5. If the method of applying the patent range i is the method of the patent, the average knife amount of the _, /, γ bismuth agent is 100000 or more. 6. If the method of applying the patent range i, the +, p,. A &quot ; Hai I caller dosage range is 100 grams of the titanium-ruthenium template synthetic gel system 〇 (9) (1) to 0.05 grams. 19 Π 1321 201119738 r 7. The method of claim 5, wherein the flocculant system It is added in the form of an aqueous solution of a coagulant. 〃 8· ^ The method of applying the patent formula (4), wherein the concentration of the flocculant aqueous solution is 0.1 to 1 weight 〇 / 〇. 9. 2 Patent Application (4), the method of the item, wherein The coagulant is selected from the group consisting of one or more selected from the group consisting of phthalate esters and polyethoxylates. A coagulant consisting of a mixture of decane and cerium oxide colloidal solution. / The method of the first method of the patent of the patent, wherein the amount of the coagulant is in the range of 1 gram of the titanium-dream template synthesis According to the method of applying the range of the method, wherein the weight ratio of the first-order crystalline particle molecular sieve to the titanium-ruthenium template synthetic rubber is between 1:10 and 1:800. The method for preparing the patent scope of each month, the towel, the titanium-stone templating agent synthetic gel is formed by the following steps: taking a titanium source in a nitrogen sealed reactor; adding a gluten to the nitrogen seal The reactor is mixed and mixed; the isothermal solution is dropped into the nitrogen sealing reactor and mixed; the plate is dropped into the nitrogen sealing reactor and mixed; and the solvent is removed to form a titanium-ruthenium template synthetic rubber. Shishen. The method of the 12th patent range of the patent, wherein the titanium source is a tetrasyl titanate. The method of the patent scope is the second method, wherein the source is a tetraalkyl phthalate. 20 111321 201119738 • I5·If the method of applying for the scope of patent 12 is Wherein, the solvent is anhydrous isopropanol. The template is the titanium source and the source of the anhydrous isopropanol. 16. The method of claim 12, wherein the propyl hydroquinone ammonium. The method of the third paragraph of the patent scope, wherein the molar ratio is between 0.005:1 and 〇.〇6:1. 18', as in the method of claim 15, wherein the molar ratio is between 1 and 1 : 1 to 4.5 : 1. The templating agent and Shi Xi 19. The method of claim 12, wherein the molar ratio is between 0.1:1 and 0.5:1. 20. For example, apply for a patent (4)! The method of the invention, wherein the water system is between 100 and 22 (the range of the TC. ... ^ ^, as in the method of applying the patent scope!, t, the time of the hydrothermal step is between 72 and 240 hours Scope 22: The method of applying for the scope of the patent item is included in the hydrothermal step (4). The steps of washing, drying and calcining are carried out. 玖: The method of the range of w is the method of making the large particle size The average particle size of the sub-screen is greater than 5 microns. 24. The cofferdam is made by "make the method: the method is based on the application of the patent media" under the condition of the age, the surface (10): the reaction reacts to form a ring Ketone oxime. 铽 虱 仃 · · · 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 The method of 5% is the same as the molar ratio of 0.7:1 to 2.0: 1. 27. The method of claim 24, wherein the solvent is used. The hydrogen peroxide and the ring are polar. The method of item 27, wherein the method comprises a group consisting of an alcohol, a ketone and water. The method of claim 24, wherein the butanol is the solvent. The solvent is the third. 30. The method according to the patent application, the quantity 'total weight of the reactants, 24, wherein the catalyst is used. Accounted for 0.1 to 10% by weight.]]]32J 22 201119738 IV. Designation of representative drawings: (1) The representative figure of the case is: No. (2) The symbol of the symbol of the representative figure is simple: No. There is no picture in this case. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: 111321